Process for hydrotreating heavy hydrocarbons and catalyst used in said process

Abstract

Spherical particles of alumina are prepared by agitating a slurry of solids comprising rehydratable alumina solids in water with a hot immiscible liquid to disperse droplets of the slurry in a continuous phase of the immiscible liquid. The droplets are shaped by interfacial surface tension and are hardened by heat while in the immiscible liquid, then are separated and calcined to produce finished spherical alumina beads. The preferred beads are of size less than one millimeter. These are used as supports for catalysts that are used in several oil refining processes such as hydrotreating for removal of sulfur or for reforming or cracking.

We claim: 
     
       1. Hydrotreating catalyst comprising at least one catalytic metal selected from group VI and, optionally, at least one promoter metal selected from Group VIII of the periodic table, on catalyst support particles consisting essentially of spherical alumina beads consisting essentially of 70 to 100% by wt of alumina that has been rehydrated from partially dehydrated alumina in the forming of said beads and has then been calcined to convert the alumina to essentially anhydrous alumina, said beads having average particle diameter in the range from about 0.1 to 1 mm, and total pore volume in the range from 0.75 to 1.3 ml/gm with 0.3 to 0.6 ml/gm of said pore volume in pores having radius less than 105 Angstroms. 
     
     
       2. Hydrotreating catalyst defined by claim 1 wherein the defined catalytic metal is molybdenum and said promoter metal is selected from cobalt and nickel or both. 
     
     
       3. Hydrotreating catalyst defined by claim 1 wherein the defined spherical alumina beads have average particle diameter less than 1 mm. 
     
     
       4. Hydrotreating catalyst defined by claim 1 wherein the defined beads are of particle size 20-40 mesh. 
     
     
       5. A process for hydrotreating hydrocarbon liquids comprising contacting said liquids with hydrogen in presence of a catalyst defined by claim 1 under hydrotreating conditions for removal of sulfur compounds, nitrogen compounds or metals or for conversion of heavy hydrocarbon components of said liquid to lighter hydrocarbon components, or any combination thereof. 
     
     
       6. A process defined by claim 5 wherein the defined contacting is carried out in an ebullated bed of the defined catalyst particles. 
     
     
       7. A process defined by claim 5 wherein the hydrocarbon liquid treated is heavy residual oil. 
     
     
       8. A process defined by claim 5 wherein the hydrocarbon liquid treated is oil derived from coal. 
     
     
       9. A process defined by claim 5 wherein the hydrocarbon liquid treated is oil derived from shale. 
     
     
       10. A process defined by claim 5 wherein the hydrocarbon liquid treated is oil derived from tar sands. 
     
     
       11. A method of making spherical alumina beads defined by claim 1 said method comprising feeding one part by volume of an aqueous slurry containing 40 to 60 percent by wt of finely divided solids which comprise 70 to 100 percent by wt of said solids of partially dehydrated rehydratable alumina powder, and at least two parts by volume of a water immiscible liquid to an agitating mixer and agitating the mixed feed with sufficient agitation to disperse said aqueous slurry as a discontinuous phase of aqueous slurry droplets in a continuous phase of said water immiscible liquid, and heating the dispersed droplets in said dispersion sufficiently to cause at least partial rehydration and hardening of the rehydratable alumina in said dispersed droplets as said droplets are shaped to spherical beads by interfacial surface tension forces in the dispersion, curing said beads with heat sufficient for rehydration of said alumina, either in said dispersion or in a separate contact with steam or water, to complete the rehydration of said alumina and calcining the rehydrated alumina beads to convert the alumina to essentially anhydrous alumina. 
     
     
       12. A method defined by claim 11 wherein the degree of agitation applied to the defined combined liquids is selected to form beads as defined having average bead diameter in the range from 0.1 to one millimeter. 
     
     
       13. A method defined by claim 11 wherein the aqueous slurry droplets are dispersed in the oil phase by an in-line motionless mixer. 
     
     
       14. Hydrotreating catalyst comprising at least one catalytic metal selected from Group VI and, optionally, at least one promoter metal selected from Group VIII of the periodic table, on catalyst support particles consisting of spherical alumina beads made by the method defined by claim 11. 
     
     
       15. A process for hydrotreating hydrocarbon liquids comprising contacting said liquids with hydrogen in presence of a catalyst defined by claim 14 under hydrotreating conditions for removal of sulfur compounds or nitrogen compounds or metals or for conversion of heavy hydrocarbon components of said liquid to lighter hydrocarbon components, or any combination thereof. 
     
     
       16. Hydrotreating catalyst comprising at least one catalytic metal selected from Group VI and, optionally, at least one promoter metal selected from Group VIII of the periodic table, on catalyst support particles consisting of spherical alumina beads made by the method defined by claim 12. 
     
     
       17. A process for hydrotreating hydrocarbon liquids comprising contacting said liquids with hydrogen in presence of a catalyst defined by claim 16 under hydrotreating conditions for removal of sulfur compounds or nitrogen compounds or metals or for conversion of heavy hydrocarbon components of said liquid to lighter hydrocarbon components, or any combination thereof. 
     
     
       18. Hydrotreating catalyst comprising at least one catalytic metal selected from Group VI and, optionally, at least one promoter metal selected from Group VIII of the periodic table, on catalyst support particles consisting of spherical alumina beads made by the method defined by claim 13. 
     
     
       19. A process for hydrotreating hydrocarbon liquids comprising contacting said liquids with hydrogen in presence of a catalyst defined by claim 18 under hydrotreating conditions for removal of sulfur compounds or nitrogen compounds or metals or for conversion of heavy hydrocarbon components of said liquid to lighter hydrocarbon components, or any combination thereof. 
     
     
       20. In a method of making spherical alumina beads comprising dispersing droplets of an aqueous slurry of alumina in a continuous phase of water-immiscible liquid and forming the droplets into spherical shaped alumina beads while dispersed in said continuous phase and sufficiently hardening said beads, while they are dispersed in said continuous phase sufficiently so that the beads will hold the spherical shape when removed from said water-immiscible liquid, the improvement wherein said dispersion of droplets is formed by feeding aqueous slurry of alumina and a water-immiscible liquid together to an agitating mixer and agitating the mixed feed with sufficient agitation to disperse the aqueous slurry as a discontinuous phase of aqueous slurry droplets in a continuous phase of the water-immiscible liquid. 
     
     
       21. An improved method defined by claim 20 wherein the defined agitating mixer is an in-line mixer having opposed stators inside a tube and wherein a mixed stream of the immiscible liquids is fed through said in-line mixer with sufficient velocity to disperse the aqueous slurry in the water-immiscible phase upon agitation of the stream by the stators inside said tube. 
     
     
       22. An improved method defined by claim 21 wherein the droplets of aqueous alumina slurry, while shaped into spherical beads in the water-immiscible continuous liquid phase, are hardened to said shape by heat. 
     
     
       23. An improved method defined by claim 21 wherein the droplets of aqueous alumina slurry, while shaped into spherical shape in the water-immiscible liquid, are hardened to said shape by ammonia in the water-immiscible liquid phase. 
     
     
       24. An improved method defined by claim 21 wherein the proportion of water-immiscible liquid to aqueous slurry of alumina and water-immiscible liquid fed to the defined agitating mixer is at least two volumes of water-immiscible liquid to one volume of aqueous alumina slurry. 
     
     
       25. An improved method defined by claim 24 wherein the defined proportion is in the range from 5 to 20 volumes to one.